Process for removing polyvinyl halide residues from processing equipment

ABSTRACT

A PROCESS FOR REMOVING RESIDUES OF POLYMERIC MATERIALS PARTICULARLY VINYL HALIDE HOMOPOLYMERS FROM PROCESSING EQUIPMENT BY A SOLVENT CLEANING TECHNIQUE BASED UPON CONTACTING SUCH RESIDUES WITHIN THE EQUIPMENT WITH N-METHYL PYRROLIDONE AND THEREBY LOOSENING, SUSPENDING OR DISSOLVING SAME. THE CONTACTING OPERATION IS PREFERABLY BY MEANS OF A SPRAY APPLIED AT ELEVATED TEMPERATURES. PROVISION IS MADE FOR RECYCLING THE SOLVENT AND RECOVERING THE SOLVENT AND/OR THE POLYMERIC RESIDUES.

United States Patent O 3,764,384 PROCESS FOR REMOVING PQLYVINYL HALIDE RESIDUES FROM PROCESSING EQUIPlVIENT Rene P. Berni, Oradell, N.J., assignor to GAF Corporation, New York, N.Y. N Drawing. Filed July 24, 1970, Ser. No. 58,201

Int. Cl. B0811 3/08, 3/10, 9/08 US. Cl. 134-12 Claims ABSTRACT OF THE DISCLOSURE A process for removing residues of polymeric materials particularly vinyl halide homopolymers from processing equipment by a solvent cleaning technique based upon contacting such residues within the equipment with N-methyl pyrrolidone and thereby loosening, suspending or dissolving same. The contacting operation is preferably by means of a spray applied at elevated temperatures. Provision is made for recycling the solvent and recovering the solvent and/ or the polymeric residues.

FIELD OF THE INVENTION The invention is directed to a novel system for the removal of residues of polymeric material which accumulate within and upon the surfaces of the polymerization equipment. In particular, the present invention is directed to the removal of such residues utilizing a unique recycling solvent system including N-methyl pyrrolidone.

BACKGROUND OF THE INVENTION AND PRIOR ART The continuing build-up of residual polymeric materials in the polymerization reactors and in and upon associated equipment after the removal of the charge in batch processing and during continued operation in continuous processing poses problems. The problems are threefold, (1) the residues, inasmuch as they are'continually exposed to the polymerization conditions, tend to vary in molecular weight beyond the intended ranges of the primary operation, and often, as the molecular weight increases, the residues become embrittled and flake off into the primary product; (2) the efficiency of the reaction is reduced since the build-up of the residues on the surfaces of the processing equipment reduces its heat-transfer capabilities and overall process control; and (3) the residues often dangerously clog the emergency venting equipment for providing relief should runaway pressures ensue within the reaction vessel. Ultimately these factors require complete shutdown of the operation for extended periods for cleaning the equipment. This, of course, leads to reduced operating efficiency and reduction in overall production.

The cleaning operation can be accomplished either mechanically or chemically. Mechanical cleaning requires dismantling of the equipment and the introduction of a cleaning crew within the reactors to manually chip the residues of polymerized material from the inner surfaces of the vessels. This is time-consuming, expensive and is hazardous to the workers engaged in the operation due to the explosive and toxic nature of many of the reactants and solvents involved in the polymerization reactions. The uniformity of protective coatings upon the surfaces of the reaction vessels may also be destroyed by chipping or the physical nature of the surfaces of the reaction vessels may be so altered as to catalyze undesirable side reactions by exposure to the underlying metals.

The chemical cleaning methods used heretofore have certain drawbacks due to the inherent nature of the chemicals used. A method based on methylene dichloride and kerosene has been proposed. This mixture loosens the bond at the reaction vessel surfaces between the reaction vessel and the residual polymeric material. The loosened ice material is then washed from the surfaces by agitating the mixture and then draining the mixture with its suspended contaminants from the vessel.

Several solvents for the polymer residues have also been proposed for cleansing wherein the reaction vessels are filled with the solvent and the residues dissolved therein. Thereafter the solution is removed from the reaction vessel by draining. The previously proposed solvents and solvent systems while moderately effective, each have had some significant drawbacks. The solvents were either explosive, formed gels with the polymer thus causing pumping difficulties or left their own residues as foreign matter. Such foreign matter in and on the reaction vessel surfaces had a tendency to degrade the quality of succeeding batches of the polymer. Additionally, often such contaminating solvents because of their irritant factors downgraded the final polymer or rendered it unfit for certain premium uses.

SUMMARY OF THE INVENTION The instant invention according to one aspect, comprises contacting the polymeric residue contaminants accumulated on the inner surfaces of the polymerization equipment with heated N-methyl pyrrolidone or a solvent system containing N-methyl pyrrolidone in major proportions for a sufficient time to loosen and/or dissolve said accumulations. The solvent containing the polymeric material is then discharged from the reaction vessel being cleaned. The discharged solvent may then be used in further cleaning processes or if sufficiently loaded with polymer residues, subjected to a regeneration process according to another aspect of this invention so as to remove the dissolved polymerization reaction residues and the regenerated solvent is then recycled to the cleaning system.

The process of the instant invention is useful for cleaning the reaction apparatus employed in the polymerization of polymers, particularly for the vinyl polymers including the polymers of vinyl halides and their copolymers. The polymers for which this cleansing system is particularly elfective include, for example, the vinyl chloride polymers and copolymers thereof with any one of the numerous monomers. The particular monomer employed for the copolymerization with the vinyl halide is not critical to the instant invention and may be exemplified by vinyl acetate, vinyl laurate, alkyl acrylates, alkyl methacrylates, alkyl maleates, alkyl fumarates, vinylidene chloride, acrylonitrile, vinyl alkyl ethers such as vinyl acetyl ether, vinyl lauryl ether, vinyl myristyl ether, and the like. Furthermore, such copolymers may be a graft copolymer in which one of the constituents is polymeric in nature, while the other constituent is a monomer. Exemplary of such grafting materials are polyethylene, copolymers of ethylene, vinyl acetate, and others. Furthermore, the instant invention is applicable in connection with other polymeric residues such as nylon C, polyesters, polyurethanes, polyacrylonitriles, polyacrylates, polymethacrylates, and copolymers and/or graft polymers thereof.

As previously mentioned, the prior art techniques have had various drawbacks including the toxicity of the sol vents, the danger of explosion or fire and the inherent toxicity and the corrosive nature of many of the previously employed solvents or reactants. The N-methyl pyrrolidone of the present invention is particularly useful and well suited for the solvent cleaning of polymerization reaction vessels due to its excellent solubility characteristics for the polymeric residues. It has inherently suitable explosiveand corrosive-resistant characteristics and most importantly has an extremely low irritant index for personnel exposed thereto. Furthermore, the material is completely non-corrosive to the various com- According to the preferred process of the instant inmonly used "reaction vessel materials and will not and vention, the solvent N-methyl pyrrolidone is drawn from a does not effect the surface characteristics thereto in any clean solvent storage tank and pumped through a heating manner likely to interfere with the course of the polymunit which serves to elevate the temperature thereof. The erization reaction. solvent may be used over a broad range of temperatures of Normally, one would not think of using N-methyl from about 75 to 150 C. Preferably, however, the solvent pyrrolidone as a solvent for systems of this type when is heated to a temperature of from about 85 to about one compares the costs of the material of this invention 125 C. Subsequent to the heating, the solvent is then with the previously used solvents. However, due to eifisprayed into the reactor by any convenient technique. cient regeneration procedures herein provided for remov- The N-methyl pyrrolidone solvent for this invention ing the dissolved residues from the solvent, it is possible may b dil t d ith minor pfopoftigns of any of h to economically reeover and recycle almost all of the mon solvents for the polymeric residues previously used y pyrrolidone Solvent for repeated rehsein the art but such dilution is not preferred as it introduces cause of its low-vapor pressure and h gh boiling Point, many of the drawbacks associated with such solvents and P1118 is recoverable In addltlfmi contrast to many raises problems in subsequent regeneration of the solvent Prevlously used solvent systems It does not form azeo by evaporation, fractional distillation or other procedures.

tropic mixtures with water. The discovery of the low-loss extraction and purification procedure permits reuse of N-methyl pyrrolidone at economical rates that are competitive with and economically more attractive than other proposed systems.

There have been numerous other solvents proposed It has been found that up to 5% of water will be picked up by the N-methyl pyrrolidone in the course of its recirculation through the polymerization equipment. Most of this results from residual moisture in such equipment from the polymerization process. Its entrance into the for use in dissolving the polymeric residues in reaction N'nlethyl pyrmhdone, m Such, Small amounts not (161' vessels such as, for example, trimethylene oxide, tetrai to tha solvatmg efficlency of the N'methyl P methyl urea, dimethylacetamide, tetrahydrofuran, cyclorohdonehexanone, cyclopentanone, cyclohexene oxide, diethyl In general it is Preferred to introduce the Nmethyl acetamide, diethyl formamide, dimethyl formamide, tetrapyrrolidone into the Polymerization apparatus at elevated hydropyran ethylene oxide, methyl ethyl ketone, dioctyl temperatures- The higher the temperature, the more p phthalate, dioxane, and many others. Such solvents vary, 3 it dissolves the Polymeric fesidues- However, at too however, in effective dissolution strength against the g temperatures, the Vapor Pressure of the N"methyl higher molecular weight of the polymeric contaminant pyrrolidone will be high enough to cause significant solto be dissolved. Furthermore, such other solvents suffer vent losses. At too low temperatures, the solvent times are f m Serious disadvantages With regard to one Or more too long for eificient industrial cleansing operations. Genof their toxicity, flash point, and explosive characteristics, erally, the temperature of the N-methyl pyrrolidone as as may be seen from the following table, wherein comintroduced into the reaction vessel should be in the range parisons of such characteristics are made between the of 150 C., with the range of l25 C. preferred solvent of the instant invention, i.e., N-methyl pyrroliand the range of 105 C. is optimal. It is expedient to done, and methylethyl ketone, cyclohexanone, and tetramaintain the temperature of the polymerization equiphydrofuran: 40 ment being cleansed within these temperature ranges. By

SOLVENT COMPARISON CHART Solvent M-pyrol MEK Oyclohexanone Tetrahydrofuran Boil point, F 395 174 315 151.

Estimated solvent recovery, percent. 1 93 Ease of separation of resifi Flash point, F.:

TAG open cup 204"... Cleveland open cup Threshold limit value (MAC). p.p.m l 200 0 Eye irritation studies (equivalent seconds) 180, 199 77 7t). Viscosity of PVC solution (10% solids) c p 151 F 116... Gels Insoluble 44 (8% solids). 212 F 34 Gels Explosive limits (percent by volume in air at 25 (1).-.. N:egligible, 0 at Negligible, 1.1 at C 1.8-11.8.

. .9 at C. Tendency to form peroxides during solvent recovery No No No Yes. Water/solvent azeotrope formation No".-. N0 Quantity of solvent used per percent of reactor volume 10-25 50 50 50.

1 Estimated value based on inhalation and other toxicity studies.

As may readily be seen from an analysis of the foregoing table, the solvent of the instant invention, i.e., N-

maintaining these temperature ranges in the polymeriza- 60 tion equipment, little additional heating is necessary durmethyl pyrrolidone, is superior to other previously recoming the recycling of the solvents from the bottom of the mended solvents and, therefore, is particularly welltank to the spray heads at the top of the tank. suited for use in connection with the instant invention. Operating within the preferred ranges, the solution of That is to say, that N-methyl pyrrolidone, because of its the residues is completed within 10-60 minutes. At the high flash point, solubility rate for high molecular weight 60 optimum range, successful cleansing of all types of polympolymeric contaminants, and high safety factor, has been erization equipment has been completed within 2040 found to be extremely useful in the process of the instant minutes for various types of polymerization residues. At invention. Furthermore, it is noted that said N-methyl temperatures below about 90 C., longer times are needed pyrrolidone is particularly well-suited for the subject 70 but even at 40 C., the polymerization residues from process as it does not form an azeotrope with water and various polymerization processes are removed within four is therefore easily separated therefrom. Furthermore, he hours by exposure to the N-methyl pyrrolidone.

cause of the low vapor pressure of said compound and The exposure and contacting of the polymerization resiits high boiling point, 98 %l]- of the N-methyl pyrrolidone due to the N-methyl pyrrolidone solvents can be eifected in used is recoverable. These features lower the cost of the various ways. The residues can be covered with the liquid use thereof relative to other such solvents. body which is then agitated in order to achieve solution,

The residues can also be subjected to streams of the liquid solvent. The residues preferably can be impacted by'inrpinging liquid particles to achieve solution as well as dislodgement, for later solution, is thus achieved.

The polymerization equipment can, of course, be filled with solvent which is then agitated until the residues are dissolved. This method requires inordinately large amounts ofj'solvent. The solvents may also be streamed over the surface of the'equipment having accumulated polymeriza'tion residues from nozzles or similar solvent access meansm is preferred to introduce the N-methyl pyrrolidone into the polymerization equipment as impinging liquid particles by spraying the N-methyl pyrrolidone from retractable spray heads into the upper portions of the polymerization equipment.

Spray heads which will generate circular spray patterns that will insure complete coverage and impingement of the s'pray upon all residue-bearing surfaces are preferred. The spray impingement upon the residue rapidly dissolves the accumulated layers or particles of the residues and thesolution flows to the bottom of the polymerization equipment. The'drainage of thedissolved and/or dislodged residue in the solvent is permitted to accumulate at the lower portions of the polymerization equipment where dislodged particles may dissolve and from where it" is pumped via surge tanks and recirculated to the spray heads. In this manner, a relatively small amount of solvent can adequately serve to dissolve and dislodge all the polymeric residues within the equipment.

*N-nietlrylpyr'rolidone is preferably used in an amount equal to at least by volume of the polymerization equipment. In order to prevent too rapid a build-up of the residues within the N-methyl pyrrolidone which may cause viscosity problems, it is expedient and economically more attractive to use 20-25% by volume of the polymerization' equipment of the N-methyl pyrrolidone. After the 'completion of the removal of the residue from one complete unit of polymerization equipment, it is then expedient and desirable to drain the residue-containing solvent from the unit, to remove the retractable heads and inse'r-t them into another unit of polymerization apparatus and successively clean such other unit. This may be continued with this volume of solvent until the residue buildup within the solvent is in the range of 1.5% to saturation of the solvent with residue. In general, it is preferred not to exceed a residue pickup by the solvent of 57%. At that solvent loading stage, it is most efl'lcient to subject the solvent to-a regeneration cycle as set forth below wherein the polymer residues are removed from the solvent and the solvent purified for reuse.

After the polymerization equipment unit is cleaned of polymerization residues as described above and the solvent drained therefrom, it is useful to wash the interior surfaces of the polymerization equipment by spraying said surfaces with a small amount of water and then permitting the water to drain from the equipment. The equipment can also thereafter beheated until dry. The unit is then ready for resumption of polymerization therein.

'When the amount of residue dissolved in the N-methyl pyrrolidone reaches 1.5 to 7%, it is desirable to regenerate, purify and recover the N-rnethyl pyrrolidone. At that time, in addition to the residue, the solvent mixture may contain up to about 8% by weight of water.

The N-methyl pyrrolidone is drained from the polymerization apparatus into a dirty solvent tank. From here, it may be directly fed to a multi-stage evaporator system or pretreated as hereinafter set forth. When fed directly to the multi-stage evaporator system, the initial stages of such a system will boil off solvent and water, concentrating the residue to'a point where the viscosity of the solution dictates the use of a mechanically-aided evaporator stage.

A preferred mechanically-aided evaporator stage is a thin'film processor operating on the turbulent film principle-although other systems designed to remove solvents from viscous solutions will also serve. The feed stream entering the unit is thrown by centrifugal force against the heated process wall to form a turbulent film between the wall and the rotary blade tips. The turbulent film covers the entire jacketed surface of the process wall at all times regardless of the evaporation rate. The viscous material is exposed to boiling temperatures for only seconds and its exposure time is controlled through feed rate and evaporation rate. A suitable device of this type is marketed by Artisan Industries, Inc. of Waltham, Mass. as a Rototherm turbulent film evaporator.

This mechanically-aided evaporator stage boils off the remaining N-methyl pyrrolidone mixture and discharges the polymeric residue, which is free of solvents, at a temperature ranging from to C. The residue at this point is of heavy mastic consistency. This material, if of satisfactory quality, may be channelled for use. If the quality is unsatisfactory, it may be directly incinerated or otherwise disposed.

If water is not present, a dehydration step is not needed. Where water in excess of 1% is present, it is best to perform a dehydration of the solvent. A fractionating system consisting of a kettle-type boiler and a fractionating tower will perform the dehydration adequately. Water vapor is discharged directly into the atmosphere at the top of the tower and the dehydrated N-methyl pyrrolidone is discharged continuously from the reboiler and returned to the clean solvent tank for reuse.

In the pretreatment alternate method for regeneration and repurifying the N-methyl pyrrolidone for reuse, the residue is first precipitated by the addition to the discharged N-methyl pyrrolidone residue solution in the tanks of 20-50% by volume of water. The precipitated polymeric residues are separated from the pyrrolidone water mixture by either filtration or via a centrifuge. The pyrrolidone/water mixture may then be fed directly to the multi-stage evaporator and from there to the dehydrator as set forth above.

With polyvinyl chloride residues, the first method of regeneration and purification is preferred. With other polymeric materials and particularly copolymers of vinyl compounds, it is often useful to first precipitate the residues. The residues are precipitated as amorphous solids. A centrifuge and/or a filter press has been found completely adequate for removal of a wide spectrum of such precipitated materials.

With both the direct and pretreatment methods, consistent recovery of at least 98% of the N-methyl pyrrolidone was obtained on an industrial scale. Such high recovery efliciency, together with the high solvating efiiciency, time efficiency and safety make the process of this invention particularly attractive and economically useful.

The term polymerization apparatus and/or equipment as used herein refers not only to the specific vessels within which polymerization occurs or is induced but includes such associated equipment upon the surfaces of which residues may accumulate. Such equipment includes fractionating columns, process lines, heat exchangers, pumps and reboilers. In each of these, the sprayed N- methyl pyrrolidone has been found to serve as an effective solvent for removing residues which accumulate therein and on the surfaces thereon.

While the term polymerization equipment and apparatus as used herein and in the examples below and is directed specifically to equipment for commercial production of polymers wherein this invention is most specifically useful, the invention is not limited thereto. The process is also useful for the cleansing of apparatus wherein reactions are carried out or liquids held which include, in addition to the normally desired reaction products, accumulated residues resulting from side reactions and which residues are solvated by the N-methyl pyrrolidone in the process of this invention. The invention thus is useful in reaction vessels .wherein N-methyl pyrrolidone-soluble side-reaction products have accumulated in and on the surfaces thereto and in the associated equipment. While such side reaction products are usually polymers, such accumulated residues on the surfaces of the vessels need not be polymers but merely soluble in the solvent for this invention to be specifically applicable thereto.

The instant invention will now be illustrated by the following more detailed examples thereof. It is to be noted, however, that the instant invention is not deemed as being limited thereto.

Example 1 The N-methyl pyrrolidone solvent was pumped into a holding tank prior to use in connection with the instant invention. Subsequent to the preparation of a polyvinyl chloride polymer, said N-methyl pyrrolidone was passed through a heat exchanger to elevate the temperature of the solvent to 90 C., pumped to retractable revolving spray heads at the top of the reactor and sprayed at a flow rate of approximately 20 to 30 gallons per minute into the 3,700 gallon, glass-lined reactor and associated process equipment to be cleaned. The reactor was filled to approximately one-quarter full with N-methyl pyrrolidone (900 gallons) and the solvent spray shut off. The solvent in the reactor was then agitated by the reactor impellers for approximately 60 minutes. The reactor temperature was maintained at 90-100 C. during this period; then the solvent-containing polymeric contaminants were pumped via the heat exchanger and spray apparatus into a second (3,700 gallon) reactor to be cleaned and the above procedure repeated. After cleaning this second reactor, the used solvent was passed to a system for the regeneration thereof. (N-methyl pyrrolidone in practice does not need to be regenerated until the polymeric residue load in the solvent reaches 1.5 to 5.0%.) As a result of the foregoing cleaning process, it was found that the N-methyl pyrrolidone dissolved and dislodged all visible polyvinylchloride residues which had accumulated on the vessel walls and further that any polyvinylchloride dislodged by the hot spray was dissolved in the agitated hot N-methyl pyrrolidone so as to effect the complete cleaning of the reactor. After draining, the reactor was spray rinsed with Water and returned to polymerization service.

Example 2 The above procedure Was repeated in the reactor after it was employed for the preparation of polymers and copolymers comprising vinyl acetate, alkyl acrylate, vinyl acetyl ether, and graft copolymers of polyethylene, copolymers of ethylene, and homopolymers of methacrylate, acrylate, and acrylonitriles. The reactor was found to be cleaned as a result of the action of the Nmethyl pyrrolidone sufiiciently for use without contamination from previous batches.

Example 3 The N-methyl pyrrolidone after cleaning the reactors as in Example 1 was heated to 90 C. and pumped into a holding tank containing a volume of well-agitated ambient temperature water equal to about 25% of the volume of N-methyl pyrrolidone. The polyvinyl chloride present in the N-methyl pyrrolidone precipitated in a fine amorphous, non-tacky form. The precipitate was then separated from the aqueous N-methyl pyrrolidone by means of a centrifuge and the precipitate was then compressed to remove any residual N-methyl pyrrolidone/ water solution present therein. Ninety pounds of polymeric residue were thus removed from two reactors by this solvent (3,700 gallon polymerization unit). The separated 8 Example 4 The regenerated N-methyl pyrrolidone of Example 3 was passed into a previously vacuum-purged polyvinylchloride reaction kettle and condenser train (3,700 gallon capacity) reactor unit. The solvent, prior to entry thereto, was passed through a heat exchanger so as to heat same to a temperature of approximately C. The solvent was pumped into the reactor and its associated reflux condenser by a revolving spray nozzle at a rate of approximately 40 gallons per minute. The spray was permitted to drain down the walls of the vessel and condense.'After the start of spraying of the solvent into the reactor, while the solvent drained at the bottom of the reactor, it was continuously recycled, pumped and sprayed through the reactor and its reflux condenser for a period of approximately 20 minutes, during which time the accumulated polyvinylchloride residues on the walls were dissolved in said solvent.

Subsequent to the end of the time period, the solvent, containing polyvinylchloride contaminants dissolved therein, was discharged from the reactor and passed to a second reactor unit. After the solvent had been discharged from the first reactor, the surface. thereof was sprayed with Water so as to wash down any residual solvent, containing dissolved or suspended contaminants, from the reactor walls. Subsequent to a second cleaning operation, which was carried out identically with that described above, the discharged solvent was transported for solvent recovery. As a result of the foregoing procedure, the resulting reactor units were found to be-free from residual polyvinylchloride contaminantsand. the units were returned to plant service for further batch polymerization. The recovery of N-methyl pyrrolidone, by a multistage evaporator using a thin film mechanicallyaided stage (Rototherm), followed by fractionation, yielded 98.4% recovery of the solvent. Ninety-three pounds of polymer residue was obtained at the discharge at the mechanical stage of the Rototherm.

What is claimed is:

1. A process for removing the polymeric residues of vinyl halide homopolymer production from the surfaces of polymerization equipment units upon which such residues have accumulated comprising: I

(a) contacting said vinyl halide polymeric residu bearing surfaces of polymerization equipment having residues consisting essentially of vinyl halide homopolymer polymeric residues With a solvent for said residue consisting essentially of N-methyl pyrrolidone heated to a temperature in the range of from about 75 C. to about C. in an amount equal to at least about 10% by volume of the polymerization equipment being cleaned for a period of time sufiicient to assure the removal of the accumulated polymeric residue from the surfaces of said equipment; and

(b) draining the residue-bearing solvent from said equipment, 1 whereby substantially all of the homopolymer vinylhalide polymeric residues can be removed from the surfaces of the equipment to be cleaned, said solvent being readily capable of regeneration for subsequent use in such residue 6. The process according to claim wherein prior to recovery by evaporation means the major portion of the dissolved polymerization residue is precipitated from the N-methyl pyrrolidone by the addition to the residue-containing solvent of from 20-50% of its volume of water, removing the precipitated residue from the N-methyl pyrrolidone-water mixture by separation means and then regenerating the solvent by feeding the mixture to the evaporation means.

7. The process according to claim 1 wherein the contacting is by spraying of N-methyl pyrrolidone onto the surfaces.

8. The process according to claim 7 wherein the spraying is achieved by spray means introduced in the upper regions of the polymerization equipment and oriented to spray said solvent onto all residue-bearing surfaces of said equipment.

9. The process according to claim 7 which further includes the steps of spraying the heated residue-containing solvent into further units of polymerization equipment and respraying such residue-containing solvent into such further polymerization equipment units until the concentration of the polymeric residues in the solvent is in the range of 1.5% to saturation.

10. The process according to claim 9 wherein the spraying and respraying is conducted for at least ten minutes in each unit of polymerization equipment.

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BARRY S. RICHMAN, Primary Examiner US. Cl. X.R. 

